Metalliferous disazo dyestuffs containing heavy metal in complex union and a reactive triazine nucleus



United States Patent METALLIFEROUS DISAZO DYESTUFFS CONTAIN- ING HEAVY METAL 1N COMPLEX UNION AND A REACTIVE TRIAZINE NUCLEUS Fritz Oesterlein, Basel, Switzerland, assignor to Ciba Limited, Basel, Switzerland No Drawing. Filed Oct. 6, 1958, Ser. No. 765,282 Claims priority, application Switzerland Oct. 11, 1957 7 Claims. (Cl. 260-146) in which D OH and D OH each represents the' radical of a diazo-component, advantageously of the benzene series which is bound to the azo linkage in a position vicinal to the hydroxyl group, and at least one of which radicals contains a halogen-1:3:5-triazine radical, and HO-A-OH represents the radical of a coupling component capable of coupling twice and which is bound to the azo linkages on each side in a position vicinal to the hydroxyl groups.

It will be understood from the foregoing remarks that the metal compounds of this invention are symmetrical or asymmetrical complexes, that is to say, they contain two identical or different disazo-dyestufis of the Formula 1. The disazo-dyestuffs present in the complex metal compounds may themselves be of symmetrical or asymmetrical structure.

The complex metal compounds of ths invention can be made by treating with an agent yielding chromium or cobalt the appropriate metal-free dyestufls which contain a triazine radical as defined above.

Advantageously, the complex metal compounds of this invention are made by condensing with one another (a) ,a complex metal compound of a metalliferous disazodyestutl Which contains a sulfonic acid group and contains, permetallisable group, one-half atom of heavy metal bound in complex union to a disazo-dyestutf of the formula ll N lkalogen in which Y represents an alkyl or aryl group, or an etherified hydroxyl or mercapto group or advantageously an amino group which may be substitued, or a halogen atom, and, if desired, at an intermediate stage or, in the product so obtained condensing one or more of the dihalogen-triazine radicals with ammonia, an organic mercaptoor hydroxy-compound or an at most secondary amine, and so choosing the relative proportions of the reactants that the final product contains at least one monohalogenor dihalogen-triazine radical.

For example, in a trihalogen-triazine, especially cyan-.

uric chloride ('2:4:6-trichloro-1:3:S-triazine), one or two halogen atoms are exchanged in such manner that one halogen atom is exchanged for the radical of a 1:2-

complex chromium or cobalt compound of a disazo-.

dyestuff of the Formula 2 which contains a disazodyestulr having an acylatable group, more especially an acylatable amino group, and that, if desired, the other halogen atom is exchanged for a free amino group or the radical of an organic compound having or not having the character of a dyestufi. Alternatively, a metalliferous:

azo-dyestutf of the kind defined above may be condensed with a 2:4-dihalogen-1z3i5-triazine which contains in.

6-position a free amino group or an organicsubst-ituent, for example, a dihalogen-triazine of the formula Y-CIJ fllHalogen l ialogen in which Y represents an alkyl or aryl group or an etherified hydroxyl or mercapto group or especially an amino group which may be substituted, in such manner that condensation takes place at the acylatable group and only one of the two halogen atoms is exchanged.

The dihalogen-triazines of the Formula 4 can be made by methods in themselves known from cyanuric halides, such as cyanuric bromide or cyanuric chloride, by reacting for example, one mol of cyanuric chloride with one mol of a reactive organic mercaptoor hydroxy: compound (for example, a phenol or an alcohol), and with one mol of ammonia or one mol of an at most secondary and advantageously a primary amine having or not having the character of a dyestufi. As such compounds there may be used, for example, aliphatic or aromatic mercapto or hydroxy-compounds, especially alcohols or phenols of low molecular weight, or methylamine, ethylamine, isopropylarm'ne, methoxyethylamine, methoxypropylamine, cyclohexylamine, dimethylamine, diethylamine or N-methyl-phenylamine, chlorethylamine, aniline, ethanolamine, piperidine, morpholine, an aminocarbonic acid ester, an aminoacetic acidethyl ester, hydrazine, phenyl-hydrazine or ammonia, or, if desired, an amine containing a group imparting solubility in water, such as an aminoethane sulfonic acid, aminoacetic acid, N-methylamino-ethane sulfonic acid, ortho-, metaor para-aminobenzoic acid, an aminosalicylic acid, an aminobenzoic acid sulfonic acid, an aminobenzene sulfonic acid such as ortho-, metaor paraaminobenzene sulfonic acid, or an aminonaphthalene sulfonic acid, or an amino-monoazo-dyestufl or other amino dyestuff, for example, of the xanthoue, thioxanthone or anthraquinone series.

The metalliferous starting dyestufis to be used for condensation with the halogen-triazines of the Formula 3 or 4 can be made by methods in themselves known, for example, by using disazo-dyestuffs of the Formula 2 which contain, in addition to the orthozorthd-dioxy-azo; groupings capable of forming metal complexes, at least one acylatable group, more especially an acylatable Patented May 31, 1960 l V s 3 amino group,.that is to say, a primary or secondary ammo group, which is bound directly to one of the external nuclei of the dyestuff molecule. Such metallisa'bledisazo-dyestuffscan'be obtained by the reduction pounds of the benzene series containing an acylamino.

group or a nitro group and coupling components capable of coupling'twice in positions vicinal to two hydroxyl groups. As examplesvof suitable coupling components there may be mentioned di-(aceto-acetylamino)-benzen'es,,. di(acetoacetylamino)-diphenyl, di-(acetoacetylo)-stilbene, stilbene-dipyrazolones, :5'-dihydroxy- 2:2'dinaphthyl-urea-7:7'-disulfonic acid, and more especially 5 :5 dihydroxy-2:2-dinaphthylamine-7 :7-disul fonic acid. As examples of suitable diam-components there may be mentioned 1-hydroxy-2-amino-6-acetylaminobenzene-4-sulfonic acid,. l-hydroxy-2-amino-4-nitIo-acetylaminobenzene, 4-nitro-2-aminophenol-6-sulfonic acid or 6-nitro-2-aminophenol-4-sulfonic acid. The hydrolysis of the metallisable disazo-dyestuffs containing an acylamino group, obtainable from the aforesaid components, can be carried out during'or after metallization of the'dyestuff. p 7 I The conversion of the dyestuffs obtained from the aforesaid components into the complex metal compounds to be used as starting materials in the process of this invention may be carried out while the dyestuffs are present in the coupling mixture.

The treatment with the agent yielding chromium or cobalt is carried. out in such manner that there is obtained a chromiferous or cobaltiferous dyestuif containing, per metalizable grouping, one-half atom of chrornium or cobalt bound in complex union.

Accordingly, the metallization is advantageously carried out with such an agent yielding chromium or cobalt and by such a method that a complex chromium or cobalt compound of the aforesaid constitution is obtained. For this purpose it is generally of advantage touse less than two and advantageously about one atomic proportion of chromium or cobalt for each molecular proportion of dyestuff and/or to carry out the metallization in a weakly. acid to alkaline medium. Accordingly, there are especially suitable for carrying out the process those chromium or cobalt compounds which are stable in alkaline media, for example, complex chromium or cobalt compounds of aliphatic hydroxy-carboxylic acids orudicarboxylic acids, or complex chromium or cobalt compounds of aromatic ortho-hydroxycarboxylic acids.

7 As examples of aliphatic hydroxy-carboxylic acids or dicarboxylic acids there may be mentioned, inter alia, lactic acid, glycollic acid, citric acid and especially. tar.-

A a temperature and Y cases it is possible to prepare dry preparatrons d rectly mixture in which the dyestufi taric acid, and among aromatic ortho-hydroxy-carboxylic acids there may be mentioned, for example, those of the benzene series such as 4-, 5- or 6-methy1-l-hydroxybenzene-2-carboxylic acid and especially l-hydroxybenzenecarboxylic acid itself. As agents yielding cobalt there may be used, however, simple compounds of 'divalent cobalt, such as cobalt acetate or cobalt sulfate or, if desired, cobalt hydroxide.

The conversion of the dyestuffs into the complex chromium or cobalt compounds is advantageously carried out at a raised temperature under atmospheric or superatrnospheric pressure, for example, at the boiling temperature of the reaction mixture, if desired, in the pres ence of a suitable addition, for example, a salt of an organic acid or of a base or an organic solvent or other agent capable of assisting the formation of complexes.

' A unitary dyestufi may be subjected tothe aforesaid metallization. However, it is also possible and in many rations are obtained cases of advantage, for example, for producing various shades of color, to metallize a mixture of two diiferent metallizable disazo-dyestufis as defined above.

The condensation of the aforesaid complex metal compounds of disazo-dyestuffs with cyanuric chloride or with a dihalogen-triazine of the Formula 4 is advantageously carried out in the presence agent, such as sodium acetate, sodium hydroxide or sodium carbonate and under conditions such that at least one exchangeable halogen atom remains in the finished product per triazine nucleus, that is to say, for example, by working in the presence of an organic solvent or at a relatively low temperature in an aqueous medium.

The new dyestuffs ofthis invention are suitable for dyeing or pr inting a very wide variety of materials, especially polyhydroxylatedifibrous.materials, such as cellulosic materials and also synthetic fibers, for example, of regenerated cellulose, or natural materialsgfor example, cellulose, linen'or above all cotton. 'They are suitable for. dyeing by the so-called direct dyeing methods, from alkaline aqueous baths which may have a high concentration of a salt, and especially by printing or pad dyeing processes in which the dyestuif is applied to the material to be dyed by printing or foularding and fixed on the fiber by means of an agent capable of binding acid, if desired, under the action of heat.

The dyestuffs so obtained are preferably isolated at a low temperature, for example, by salting out and filtrationyorby evaporating the mixture in which they are prepared. The filtereddyestuffs may be dried, if desired, after the addition of an extender or stabilizing agent. Advantageously the drying is carried out at not too high under reduced pressure. In-some by spray drying the whole 7 is'prepared, that is to say, without intermediate isolation of the dyestuff. In this manner valuable new dry prepawhich are suitable for preparing stock solutions or dyebaths or, if desired, printing pastes.

Dyeings produced on cellulosic fibers with the dyestuffs of this invention are generally distinguished by their good fastness to light and above all by their excellent fastness to washing. 7

The following examples illustrate the invention; the parts and'percentages being by weight unless otherwise stated and the relationship of parts by weight to parts by volume'being the same as that of the kilogram to the liter:

Example 1 48.7 parts of the disazo-dyestufi obtained by coupling diazotized 1 -hydroxy 2 amino 6 acetylarnino 4 sulfonic acid in an alkaline medium with 5 :5-dihydroxy- 2:2-dinaphthylamino-7:7'-disulfonic acid are heated in 800 parts of a sodium hydroxide solution of 4% strength for one hour at -95 C. to hydrolyse the acetylamino group. After neutralizing the mixture with hydrochloric acid to a pH value of 8, parts'of a solution of sodium chromosalicylate having a chromium content of 2.6% are added, and the whole is boiled under reflux for 4 hours.

In order toprepare the symmetrical dichlorotriazine derivative the alkaline solution of the chromium compound of the dyestuflf, which contains two azo linkages per chromium atom, is adjusted to a pH-value of 7 with dilute hydrochloric acid. 18.5 parts of cyanuric chlo ride dissolved in a small amount of acetone are added at 0.-5 C., while stirring well, and the pH-value is maintained constant at about 7 by the dropwise addition of 50 parts by volume of a 2 N-solution of sodium hydroxide. I

After the addition of 5 parts of monosodium phos phate and 5 parts of disodium phosphate, the solution is evaporated to dryness at 3040 C. in vacuo.

The new dyestuff so obtained dyes cellulose fibers of an acid binding 6 blue tints in the manner described in Example 7, which Example 3 tints have a good fastness to washing and light.

In order to produce the symmetrical monochlorotriazine derivative the procedure described in the second paragraph of this example is first carried out, and to the 5 resulting solution are added 125 parts of a 2 N-solution of ammonia and the whole is stirred for 3 hours at solution rendered alkaline with sodium carbonate, and the intermediate product so obtained is coupled with the 35-40 0. By the addition of sodium chloride the dyei 'fj fif i if f stufi is reci itated and is then filtered ofi and dried p mo '8 mm am '0 'Orm e emc P P o dyestufl, and then the acetyl group is split off by heating in vacuo at 50 C. It rs the chromrum complex com- 10 the dyesmfl, with dilute caustic soda Solution pound, containing one half atom of chromium per metal- The aminodisazmdyesmfi so obtained is condensed lizable o:o'-dihydroxyazo grouping, of the disazo dye- Stufi of the formula aqueous solution w1th 18.4 parts of cyanunc chlorid SOrH NH;

The new dyestufi dyes cellulose fibers by the method at 010 0., and the monochloro-triazine derivative so described in Example 7 blue tints which are of good formed is reacted with 120 parts of a 2 N-solution of amfastness to washing and light. monia at C. The dyestufi is salted out, filtered ofi' By using 4-nitro-6-acetylamino-2-amino 1 hydroxyand dried. It is the chromium complex compound of the benzene as diazo-component, instead of 6-acetylamino-2- disazo-dyestuff of the formula OH HO S0311 S0aH NH:

amino 1 hydroxy benzene- 4- sulfonic acid, there said chromium complex compound containing, per metalare obtained by hydrolysis, metallization, condensation lizable group, substantially half an atomic proportion of with cyanuric chloride and, if desired, reaction with chromium in complex union with said disazo-dy'estuff; it ammonia as described in this example, dichloroand 40 dyes cotton blue tints. monochloro-triazine containing chromium complex com- Dyestufis having similar properties are obtained by pounds which can be fixed on cellulose fibers to give using, instead of the diazo-compound of 6-nitro-2-aminogreenish grey tints. The corresponding complex cobalt phenol-4-sulfonic acid, the diazo compound of 2-aminocompounds of the dyestufi from 4-nitro-6-acetylamino-2- phenol-4-sulfonic acid or of 2-aminophenol-4:6-disulfonic amino-l-hydroxybenzene dye cotton fast grey tints. acid or of 1-amino-2-hydroxynaphthalene-4-sulfonic acid.

E l 2 The dyestufi from 2-aminophenol-4-sulfonic acid is the mm? 9 chromium complex compound of the disazo-dyestufi of 48.7 parts of the disazo-dyestufi obtained by coupling the formula OH HO OH I HO N N=N N= NH-(l) o1 N N H018 SOzH \C/ 3 0311 SOQH IIH| diazotized 1 hydroxy 2 amino 6 acetylaminosaid chromium complex compound containing, per metalbenzene-4-sulfonic acid in an alkaline medium with 5:5'- lizable group, substantially half an atomic proportion of dihydroxy 2:2 dinaphthylamino 7:7 disulfonic chromium in complex union with said disazo-dyestufi. acid are heated in 800 parts of sodium hydroxide solle 4 tion of 4% strength for one hour at 90-95 C. to hyramp drolyse the acetylamino group. After adjusting the pH- The primary condensation product obtained from 17.3 value of the mixture to 9 with hydrochloric acid, 100 parts of l-aminobenzene-Z-sulfonic acid and 18.5 parts parts of a cobalt sulfate solution having a cobalt conof cyanuric chloride in known manner, is condensed with tent of 3.25% are added. After stirring the mixture for the complex chromium compound obtained as described A hour at -80 C. the formation of the cobalt comin the first paragraph of Example 1. The condensation pound is complete. is carried out in a neutral aqueous solution and at ap- The symmetrical monochloroand dichloro-triazine proximately 40 C. There is obtained a dyestufi which compounds are prepared by the methods described in Ex- 70 dyes cotton blue tints that are fast to light and washing. ample l for preparing the corresponding chromium com- Instead of the l aminobenzene-Z-sulfonic acid used for pounds. making the primary condensation product, another amine The new dyestufis dye cellulose fibers by the method may be used, for example, l-aminobenzene-B-sulfonic described in Example 7 dull violet-blue tints of good acid, 2-aminonaphthalene-4z8-disulfonic .acid, Z-aminm fastness to washing and light. naphthalene-G-sulfonic acid, l-aminobenzene-Z-carboxylie The diazo-compound of 23.4 parts of 6-nitro-2-amino-J phenol-4-su1fonic acid is coupled with 46.1 parts of 5:5'-' dihydroxy-2:2'-dinaphthy1amino-7:7'-disulfonic acid in a acid, Z-aminoethanol, 1 ethylamine, 3-methoxypropylamine, morpholine, aniline, diethanolamine. Dyestufis having similar properties are obtained with all these .By using in this example, instead of the aforesaid primary condensation product, 18 parts of 2-methoxy- 4:6-dichlorotriazine or 27 parts of 2-phenylthio-4z6-dichlorotriazine or 33 parts of 2-phenoxy-4z6-dibromolz3 z-triazine, dyestuffs having similar properties are obtained. 3

r p 1 Example 5 a 46.7 parts of the disazo-dyestufi, obtained by coupling 2 mols of diazotized 1-hydroxy-2-amino-6-acetylaminobenZene-4-sulfonic acid with 1 mol of 5:5'-dihydroxy- 2:2'-dinaphthyl-urea-7:7'-disulfonic acid in an alkaline medium and then splitting off the acetylgroup by hydrolysis with sodium hydroxide solution of 3% strength, are converted into the 1:2-complex chromium compound H in the manner described in Example 1. By the method*' described in Example 1, the complex chromium compound is condensed with cyanuric chloride, the reaction product isreacted with ammonia, and the resulting monohlorodriazine dyestufi 'is isolated. It is the chromium complex compound of a disazo-dyestufi containing per eta1lizable-group, substantially-half an atomic proportion of chromium in complex union with a disazo-dyestufi of the formula and dyes cotton dull violet-brown tints of good fastness to light and washing.

By using, instead of ammonia, ethylamine or Z-aminoethanol or methylamine dyestuffs having similar properties are. obtained. 1

v By using in this example, instead of 5.:5-dihydroxy- 2:2'-'dinaphthyl urea-7:7'-disulfonic acid, the corresponding quantity of"stilbene dipyrazolone-2:2-disulfonic acid and otherwise proceeding as described in this example, there is obtained a dyestufi which dyes cotton red-orange Example 6 1 part of the dyestufi obtainedas described in Example 1 is mixed with 6 parts of urea dissolved in 41 parts of water, and the solution is stirred into parts of an aliginate thickening of 4% strength. 2 parts of calcined sodium carbonate are added, and a cotton fabric is printed with .the resulting printing paste on a roller printing machine.

The fabric so printed is dried, then steamed for 6 minutes at IOU- 401 C. it is then rinsed, treated in a sodium'bicarbonate solution of 0.5% strength, rinsed, soaped for A hour in solution of 0.3% strength of a non ionic detergent at the boil, rinsed and dried. There is obtained a blue print which is fixed fast to boiling.

Example 7 i '2 parts of the dyestuflf obtained as described in the first .four paragraphs of Example 1 are dissolved in 100 parts'of water. A cotton fabric is impregnated with the solution on a foulard, and squeezed until it retains 75% of itsweight of dyestuff solution, vTheimpregnated fabric is then dried, and impregnated at room temperature in a-solution containing, per liter, 10 grams of sodium hydroxide and300 grams of sodium chloride, then squeezed toaweight increase of 75%, and steamed for seconds 311100-101? C. 'Thefabric is 'then rinsed, soaped tor :Vuhour :in-anaqueoussolution of,0.3% strength of a on HO on no N p l i C-NH =N- N= HOzS- nn-co-masons non-ionic detergent, rinsed and dried. There is obtained a blue dyeing fixed fast to boiling. I

Wha't'is claimed is? of 'a in which n is a Whole positive number up to 2, R OH and R -OH each represents a hydroxybenzene radical bound to the azo linkages in ortho position relatively to the hydroxyl group, one of said hydroxybenzeneradicals containing a member selected from the group consisting of 2:4-dichloro-1 :3 :S-triazine, 2-methoxy-4-chloro-1 3 :5-

triazine, 2-phe'noxy-4-chloro-1 3 S-triazine, 2-phenylthio- 4-chloro-l :3 :5 -triazine, 2-phenoxy-4-bromo-l :3 :S-triazine, and 2-chloro-4-amino-1:3z5-triazine radicals bound in its 6-position by an NH-bridge, and wherein the OHgroups indicated on the said formula'arethe sole metallizable group, said-metal complex compound containing a sulfonic acid group and, per metallizable group, substantially one-half-an atomic proportion of a heavy metal selected from theigroup consisting of chromium and'coba'lt bound in complex union with said .disazodyestuff.

- 2. A water-soluble chromium complex compound of adisazo-dyestufi of the formula in which Y represents a member selected from the group ,consisting of a hydrogen atom and a sulfonic acid group,

one X represents a member selected from the group consisting of a nitro group, a hydrogen atom and a 2- chloro-4-amino-1z3z5-triazine substituent bound by an -NH-bridge in its 6-position and the other X represents a 2-chloro-4-aminod23:5-triazine substituent bound by an -NH-bridge in its '6-position, said chromium complex compound containing, per metallizable group, substantially half an atomic proportion of chromium in complex union with said disazo-dyestufi'.

, 3. A water-soluble cobalt complex compound of a disazo dyestufi of the formula N11 son;

SO 3H in which Y represents-a'member selected from the group consisting of a hydrogen atom anda; sulfonioacid group,

one X represents a member selected from the group con-- sisting of a nitro group, a hydrogen atom and a 2-chlor0- 4-amino-l:3:5-tn'azine substituent bound by an -NH- bridge in its 6-position and the other X represents a 2- chloro-4-amino-1z3z5-triazine substituent bound by an 5 NH-bridgc in its 6-position, said cobalt complex com- 15 pound containing, per metallizable group, substantially half an atomic proportion of cobalt in complex union with said disazo-dyestufi.

4. The water-soluble chromium complex compound of SOaH the disazo-dyestufi of the formula said chromium complex compound containing, per metal- 110 on no N== NH-CIE/ N no.s NH- out 10 said chromium complex compound containing, per metallizable group, substantially half an atomic proportion of chromium in complex union with said disazo-dyestufi.

6. The water-soluble chromium complex compound of the disazo-dyestufi of the formula HO HO SIOIH said chromium complex compound containing, per metallizable group, substantially half an atomic proportion of chromium in complex union with said disazo-dyestufl.

7. The water-soluble cobalt complex compound of the disazo-dyestufi of the formula OH HO SOsH said cobalt complex compound containing, per metallizable group, substantially half an atomic proportion of lizable group, substantially half an atomic proportion of m cobalt in complex union with said diazo-dyestufi.

chromium in complex union with said disazo-dyestufi.

5. The water-soluble chromium complex compound of the diazo-dyestufi of the formula OH HO OH HO N 0m =N N= NH-('3/ o-ci N ii no. NE on:

| on: out NH,

References Cited in the file of this patent UNITED STATES PATENTS Durig et a1. Gunst Feb. 5, 1957 Nov. 11, 1958 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PatentNo. 2,938,895 May 31, 1960 I Fritz Oesterlein I It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 3, for "substitued" read substituted column 3, line 37, for "metalizable" read metallizable columns 9 and 10, lines 30 to 37, the right-hand portion of the formula should appear as shown below instead of as in the Signed and sealed this 1st day of November 1960,

(SEAL) Attest:

KARL H. AXLINE ROBERT Ca WATSON Attesting Officer Commissioner of Patents 

1. A WATER-SOLUBLE METAL COMPLEX COMPOUND OF A DISAZO-DYESTUFF OF THE FORMULA 